jo061745b_si_001.pdf (56.14 kB)
Acyclic or Long-Bond Intermediate in the Electron-Transfer-Catalyzed Dimerization of 4-Methoxystyrene
journal contribution
posted on 2006-11-10, 00:00 authored by Lauren L. O'Nei, Olaf WiestThe electron-transfer-catalyzed dimerization of 4-methoxystyrene has long been a prototypical reaction
for the study of radical cation reactivity. The different possible pathways were explored at the B3LYP/6-31G* level of theory. Both [2 + 2] and [4 + 2] cycloadditions proceed via a stepwise pathway, diverging
at an acyclic intermediate and interconnected by a vinylcyclobutane-type rearrangement. The experimentally
observed stereoselectivity of the cycloaddition was traced to relatively high barriers for isomerization,
while the previously described “long-bond” intermediate could not be located at the higher level of theory.
CPCM calculations show that the highly exothermic [4 + 2] pathway becomes kinetically more favorable
in condensed phase. Time-dependent density functional theory calculations indicate that the different
possible intermediates have very similar absorption spectra, making the unambiguous assignment of the
experimentally observed transient absorption of 500 nm to a given species difficult.